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991.
Le Clézio I Gornitzka H Escudier JM Vigroux A 《The Journal of organic chemistry》2005,70(5):1620-1629
Four dinucleotide building units of nucleic acids in which three out of six backbone torsion angles are included in a dioxaphosphorinane ring structure (D-CNA family) have been synthesized: two diastereoisomeric alpha,beta,gamma-D-CNA {cis and trans} and two diastereoisomeric delta,epsilon,zeta-D-CNA {(S(C4'),R(P)) and (S(C4'),S(P))}. The structural analysis of these conformationally restricted dinucleotides, using NMR spectroscopy and X-ray crystallography, shows that these D-CNA structural elements allow the stabilization of torsion angle combinations, alpha/beta/gamma and delta/epsilon/zeta, that are significantly different from those typically observed in canonical A- or B-form duplexes. 相似文献
992.
Boschetti F Denat F Espinosa E Tabard A Dory Y Guilard R 《The Journal of organic chemistry》2005,70(18):7042-7053
[reaction: see text] Bisaminal type compounds obtained by condensation of pyruvic aldehyde with the suitable open-chain tetraamine followed by cyclization with either dibromoethane or dibromopropane can be regioselectively quaternized by a wide range of alkylating agents. Removal of the bisaminal bridge yields the monosubstituted tetraazamacrocycle or bismacrocycle. Further functionalization allows the preparation of bifunctional ligands or trisubstituted macrocycles. The structure of six compounds was solved by X-ray diffraction, and the unexpected results are rationalized according to the molecular modeling calculations. 相似文献
993.
994.
Lemierre V Chrostowska A Dargelos A Chermette H 《The journal of physical chemistry. A》2005,109(37):8348-8355
With the help of various theoretical methods, ionization potentials (IPs) have been computed for a panel of small molecules containing atoms of group 14, 15, or 16 and representing different singly, doubly, or triply bonded systems with or without an interacting heteroatom lone pair. Comparison of experimental IP values to theoretical results indicates that (i) the standard outer valence green function (OVGF), density functional theory (DFT), and DeltaSCF methods lead to rather accurate values, (ii) the CASPT2 method systematically underestimates IPs, (iii) the method of deducing IPs from a shift of some standard DFT eigenvalue spectrum is a straightforward approach leading to rather accurate IPs, (iv) the eigenvalue spectrum obtained with the so-called statistical average of different orbital model potential (SAOP) exchange-correlation model potential is an efficient approach leading directly to quite accurate IPs, and (v) a good prediction of the IP spectrum can be obtained from the shifted excitation spectra of the system calculated by the time-dependent DFT (TD-DFT) method. It is also shown that the TD-DFT calculations of the ionized species bring a significant improvement over the calculations of the neutral molecules, indicating that a great part of the electronic relaxation is already taken into account (in a similar way for all ionizations). Finally, in the case of TD-DFT calculations of neutral molecules, the statistical average of different orbital model potential (SAOP) functional does not lead to significantly better results than the B3LYP functional. 相似文献
995.
Hexyl thiol has been transformed to hexyl selenol and related selenides and selenocyanate by substitution of the corresponding hexyldiphenylsulfonium tetrafluoroborate with selenium nucleophiles. 相似文献
996.
We study the effect of the connectivity pattern of complex networks on the propagation dynamics of epidemics. The growth time scale of outbreaks is inversely proportional to the network degree fluctuations, signaling that epidemics spread almost instantaneously in networks with scale-free degree distributions. This feature is associated with an epidemic propagation that follows a precise hierarchical dynamics. Once the highly connected hubs are reached, the infection pervades the network in a progressive cascade across smaller degree classes. The present results are relevant for the development of adaptive containment strategies. 相似文献
997.
For the first time a very weak N-N stretching band (ν5) of hydrazine was unambiguously assigned in the Fourier-transform infrared spectrum. Almost 1500 transitions with a resolution of for K′ from 0 to 6 and for all symmetry species have been analyzed. Despite some perturbations a global fit has been carried out successfully and the band center was determined at , much higher than previously expected. 相似文献
998.
Bounds on isocurvature perturbations from cosmic microwave background and large scale structure data
We obtain very stringent bounds on the possible cold dark matter, baryon, and neutrino isocurvature contributions to the primordial fluctuations in the Universe, using recent cosmic microwave background and large scale structure data. Neglecting the possible effects of spatial curvature, tensor perturbations, and reionization, we perform a Bayesian likelihood analysis with nine free parameters, and find that the amplitude of the isocurvature component cannot be larger than about 31% for the cold dark matter mode, 91% for the baryon mode, 76% for the neutrino density mode, and 60% for the neutrino velocity mode, at 2sigma, for uncorrelated models. For correlated adiabatic and isocurvature components, the fraction could be slightly larger. However, the cross-correlation coefficient is strongly constrained, and maximally correlated/anticorrelated models are disfavored. This puts strong bounds on the curvaton model. 相似文献
999.
Recent experiments [R. A. Gray, Phys. Rev. Lett. 87, 168104 (2001)]] have revealed striking standing wave patterns in cardiac muscle. In excitable media, such as cardiac tissue where colliding waves annihilate, standing wave patterns result from a fully nonlinear mechanism. We present a possible physical mechanism explaining these patterns. The phenomenon does not depend on the precise excitable model chosen. Analogies are drawn with weak links in superconductors, and phase-slip solutions in the Ginzburg-Landau equations. 相似文献
1000.
Chalcogenide glasses are promising candidates for all-optical switching and various nonlinear applications. However, we show that As2S3 thin films are photosensitive at wavelengths in the 1.5-microm telecommunication window. This sensitivity is evidenced by the formation of self-written waveguides in slabs, where channels as narrow as 1 microm are created. We also show the detrimental effects of such photosensitivity in ridge waveguides. This photosensitivity seems to occur only in thin-film form and not in bulk samples or fibers. 相似文献